Use of basalt to adsorb toxic material

ABSTRACT

Basalt selectively adsorbs organic toxic materials, such as dioxins, furans, polychlorinated biphenyls (PCBs), bis(2-ethylhexyl)phthalate, arsenic, mercury, chromium, copper, nickel, zinc, cadmium, lead, and the like, from substances such as sediment, which contains water and the toxic materials.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Nos. 62/448,552 filed Jan. 20, 2017, and 62/537,141 filedJul. 26, 2017, both incorporated herein in their entirety by reference.

FIELD OF THE DISCLOSURE

The invention relates in one non-limiting embodiment to methods andcompositions for removing toxic materials from substances such as waterand sediments, and more particularly relates in another non-restrictiveversion to methods and compositions for selectively removing toxicmaterials from sediments and water using basalt.

BACKGROUND

Chlorinated dibenzodioxins (CDDs) are a family of different compoundscommonly referred to as polychlorinated dioxins. These compounds aregenerally considered toxic and have varying harmful effects. The CDDfamily is divided into eight groups of chemicals based on the number ofchlorine atoms in the compound. The group with one chlorine atom iscalled the mono-chlorinated dioxin(s). The groups with two through eightchlorine atoms are called di-chlorinated dioxin (DCDD), tri-chlorinateddioxin (TrCDD), tetrachlorinated dioxin (TCDD), penta-chlorinated dioxin(PeCDD), hexa-chlorinated dioxin (HxCDD), hepta-chlorinated dioxin(HpCDD), and octa-chlorinated dioxin (OCDD), respectively. The chlorineatoms can be attached to the dioxin molecule at any one of eightpositions. The name of each CDD indicates both the number and thepositions of the chlorine atoms. For instance, the CDD with fourchlorine atoms at positions 2, 3, 7, and 8 on the dioxin molecule iscalled 2,3,7,8-tetrachlorodibenzo-p-dioxin or 2,3,7,8-TCDD:

2,3,7,8-TCDD, which is sometimes just referred to as “dioxin”, is one ofthe most toxic of the CDDs to mammals, and thus humans, and has receivedthe most attention. Therefore, 2,3,7,8-TCDD serves as a prototype forCDDs as a group, and thus CDDs with toxic properties similar to2,3,7,8-TCDD are called “dioxin-like” compounds. Chlorinateddibenzofurans (CDFs) are chemically related and can occur along withCDDs. Polychlorinated biphenyls (PCBs) are also chemically related.

In the pure form, CDDs are colorless solids or crystals. CDDs may enterthe environment as mixtures containing a variety of individualcomponents and impurities. In the environment they tend to be associatedwith ash, soil, or any surface with a high organic material content,such as plant leaves. In water and air, a portion of the CDDs may befound in the vapor or dissolved state, depending on the amount ofparticulate matter, temperature, and other environmental factors. CCDshave very low water solubility and tend to adsorb onto solid particles.

CDDs are known to occur naturally, and may also be produced by humanactivities. CDDs are naturally produced from the incomplete combustionof organic material by forest fires or volcanic activity. CDDs are notintentionally manufactured by industry, except in small amounts forresearch purposes. They are unintentionally produced by industrial,municipal, and domestic incineration and combustion processes. It ispresently believed that CDD emissions associated with human incinerationand combustion activities are the predominant environmental source.

CDDs (mainly 2,3,7,8-TCDD) may be formed during the chlorine bleachingprocess used by pulp and paper mills. CDDs may also occur as acontaminant in the manufacturing process of certain chlorinated organicchemicals, such as chlorinated phenols, such as during the manufactureof 2,4,5-trichlorophenol (2,4,5-TCP). 2,4,5-TCP was used to producehexachlorophene (used to kill bacteria) and the herbicide,2,4,5-trichlorophenoxyacetic acid (2,4,5-T). In most industrializedcountries the use of products contaminated with CDDs has been greatlyreduced.

One place where dioxins/furans are present is in the San Jacinto RiverWaste Pits (SJRWP) Superfund Site near Houston, Tex. The dioxins/furansin the SJRWP are from paper mill waste. It is therefore highly desirableto have an effective method for removing dioxins/furans from waste andsediment such as that found in the SJRWP and other locations thatcontain similar materials.

SUMMARY

In one aspect, the invention is a method for removing toxic materialfrom a substance, such as sediment, where the process includingcontacting a substance that comprises water and at least one toxicmaterial with an effective amount of basalt for a period of timeeffective to remove at least a portion of the at least one toxicmaterial from the sediment into the basalt, for instance by adsorption.

DETAILED DESCRIPTION

In one non-limiting embodiment, the method involves contacting asubstance, e.g. sediment, that includes or comprises at least one toxicmaterial with basalt in an effective or sufficient amount for aneffective or sufficient amount of time for the basalt to adsorb orotherwise remove at least a portion of the at least one toxic material.In one non-restrictive version of the method, the substance beingtreated comprises water and the at least one toxic material.

Although the method is expected to be useful in removing toxic materialsfrom many substances, in one particular, non-limiting embodiment, themethod removes toxic materials from sediment. “Sediment” is defined asmatter that settles to bottom of a liquid. Sediment is particulate andmay include dirt, sand, silt, gravel, sludge, dregs, lees, precipitate,deposits, mud, muck, mire, ooze, alluvium, and the like. As definedherein, sediment is not limited by particle size, although any of thesize ranges given below in Table I alone or in combination would beapplicable.

TABLE I Partial International Identification and Classification of SoilsName Size range (mm) Size range (approx. in.) Coarse soil Sand Coarsesand CSa 0.63-2.0 0.024803-0.078740 Medium sand MSa  0.2-0.630.0078740-0.024803  Fine sand FSa 0.063-0.2  0.0024803-0.0078740 Finesoil Silt Coarse silt CSi  0.02-0.063 0.00078740-0.0024803  Medium siltMSi 0.0063-0.02  0.00024803-0.00078740 Fine silt FSi  0.002-0.00630.000078740-0.00024803  Clay Cl ≤0.002 ≤0.000078740It will be appreciated that the methods discussed herein may be used toremove toxic materials from other substances besides sediments,especially particulate substances that comprise water or to which watermay be added to facilitate processing using the methods describedherein. Such substances include, but are not necessarily limited to,flowing particulates that are a by-product from a manufacturing process(whether or not the byproduct is intentionally made), polymer particlesor powders, ground water, and the like.

The sediment treated with basalt typically contains water. In onenon-limiting embodiment, the method involves the case where the water inthe sediment contains at least one water-soluble material. Becausedioxins/furans and related compounds have very low water solubility,they are adsorbed on the particles, e.g. soil, dirt, rock, etc.Contacting the sediment with basalt causes the basalt to preferentiallyor selective adsorb the dioxins/furans from the sediment, while thebasalt does not appreciably adsorb the at least one water-solublematerial. While the dioxins/furans have low solubility in water, in onenon-limiting embodiment it is believed that the liquid water facilitatesthe transfer of the dioxins/furans from the sediment to the basalt.

“Basalt” is defined herein as a common extrusive igneous (volcanic) rockformed from the rapid cooling of basaltic lava exposed at or very nearthe surface of a planet or moon. Flood basalt describes the formation ina series of lava basalt flows. In an alternative, more detaileddefinition, basalt is an aphanitic (fine-grained) igneous rock withgenerally 45-55% silica (SiO2) and less than 10% feldspathoid by volume,and where at least 65% of the rock is feldspar in the form ofplagioclase. It is the most common volcanic rock type on Earth, being akey component of oceanic crust as well as the principal volcanic rock inmany mid-oceanic islands, including Iceland, Reunion Island, and theislands of Hawaii. Basalt commonly features a very fine-grained orglassy matrix interspersed with visible mineral grains. The averagedensity is 3.0 gm/cm³.

Basalt is defined by its mineral content and texture. Physicaldescriptions without mineralogical context may be unreliable in someinstances. Basalt is usually grey to black in color, but rapidlyweathers to brown or rust-red due to oxidation of its mafic (iron-rich)minerals into hematite and other iron oxides and hydroxides. Althoughusually characterized as “dark”, basaltic rocks exhibit a wide range ofshading due to regional geochemical processes. Because of weathering orhigh concentrations of plagioclase, some basalts can be light-colored,superficially resembling andesite to untrained eyes. Basalt has afine-grained mineral texture due to the molten rock cooling too quicklyfor large mineral crystals to grow. Basalt is often porphyritic,containing larger crystals (phenocrysts) formed prior to the extrusionthat brought the magma to the surface, embedded in a finer-grainedmatrix. These phenocrysts often are of olivine or a calcium-richplagioclase, which have the highest melting temperatures of the typicalminerals that can crystallize from the melt.

Basalt can be fashioned or shaped into a wide variety of forms,including but not necessarily limited to, fibers, chopped fibers,roving, filaments, mats, strands, chopped strands, particles, pellets,textiles, fabrics, tape, yarn, mesh, wool and combinations thereof.Because the method described herein involves contacting the sedimentwith basalt, it is believed that basalt with relatively high surfacearea per volume will be more efficient at adsorbing the at least onetoxic material than basalt with relatively low surface area per volume.Suitable forms of basalt are available from United States BasaltCorporation (US Basalt).

The basalt can contain a wide variety of physical forms. For instance,in the case of waste pits, such as SJRWP, the cap and/or liner for thepit may be made entirely or partially of basalt. It is expected that thebasalt can beneficially be formed into filters, such as industrialfilters, for sediment and other substances to be pumped or passedthrough.

In one non-limiting embodiment the at least one toxic material includesdioxins, furans, and/or polychlorinated biphenyls (PCBs). PCBs arechemically similar to certain dioxins such as OCDD. A partial list ofdioxins and furans that may be removed from sediment by adsorption bybasalt is given in Table II.

TABLE II Dioxins and Furans Name Abbreviation 1,2-dioxin — 1,4-dioxin —2,3,7,8-tetrachlorodibenzo-p-dioxin TCDD1,2,3,7,8-pentachlorodibenzo-p-dioxin PeCDD1,2,3,4,7,8-hexachlorodibenzo-p-dioxin HxCDD1,2,3,6,7,8-hexachlorodibenzo-p-dioxin HxCDD1,2,3,7,8,9-hexachlorodibenzo-p-dioxin HxCDD1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin HpCDDoctachlorodibenzo-p-dioxin OCDD Furan — 2,3,7,8-tetrachlorodibenzofuranTCDF 1,2,3,7,8-pentachlorodibenzofuran PeCDF2,3,4,7,8-pentachlorodibenzofuran PeCDF1,2,3,4,7,8-hexachlorodibenzofuran HxCDF1,2,3,6,7,8-hexachlorodibenzofuran HxCDF1,2,3,7,8,9-hexachlorodibenzofuran HxCDF2,3,4,6,7,8-hexachlorodibenzofuran HxCDF1,2,3,4,6,7,8-heptachlorodibenzofuran HpCDF1,2,3,4,7,8,9-heptachlorodibenzofuran HpCDF octachlorodibenzofuran OCDF

It will be appreciated that sometimes in the specification and claimsherein the term “dioxin” is used to mean all of the toxic materialsdiscussed that are chemically related to PCBs and the like, including,but not necessarily limited to all of the dioxins, furans, CDDs, CDFs,and PCBs discussed herein; that is, “dioxin” is used as a shorthand termfor brevity.

It will also be appreciated that PCBs include, but are not necessarilylimited to, AROCLOR-1016 and AROCLOR-1260, as well as other AROCLORPCBs, available from Monsanto, now Bayer.

The toxic material may also include, but is not necessarily limited to,chemical compounds having one or more phenyl groups, such asbis(2-ethyl-hexyl)phthalate.

Additionally, the toxic material may include one or more metal,including, but not necessarily limited to, arsenic, mercury, chromium,copper, nickel, zinc, cadmium, lead, and/or combinations thereof. As iswell known, it will be appreciated that not all metals are equally toxicat the same dosage level, although many metals may be considered toxicat a high enough level.

In general terms, the effective amount of basalt to use in the methodherein is any amount that will remove at least a portion of the at leastone toxic material from the sediment onto or into the basalt. Althoughit is sometimes difficult to predict in advance an effective range forany particular sediment due to a number of variables including, but notnecessarily limited to, the kind of sediment, the kind and form ofbasalt, the temperature of the method, the contact time, the types andamounts of dioxins/furans, and the like, in one non-limiting embodimentan effective amount of basalt to at least one toxic material rangesequal to or more than about 200:1 independently to about 1:3 on a weight: weight basis; alternatively equal to or more than about 100:1independently to about 1:2; in a non-restrictive embodiment equal to ormore than about 50:1 independently to about 1:1; all on a weight :weight basis. As used herein with respect to a range, the term“independently” means that any lower threshold may be combined with anyupper threshold to give a suitable alternative range.

In another non-limiting embodiment the effective amount of time that thebasalt is contacted with the sediment ranges from about 24 hoursindependently to about 7 days; alternatively from about 2 daysindependently to about 6 days; in another non-limiting embodiment fromabout 3 days independently to about 5 days; and in anothernon-restrictive version about 60 hours independently to about 84 hours.The contacting may be conducted by any suitable technique including, butnot necessarily limited to, stirring, mixing, spraying, counter-currentflow, co-current flow, extrusion, extraction, passing the componentsthrough a static mixer, combinations of these, and the like. In somenon-restrictive versions, the time period may be open-ended, forinstance if a basalt-containing cap and/or liner is used to encompasssediment in a waste pit. Such a cap and/or liner may be in place formany years.

The method as described herein is not limited to any particulartemperature range or pressure range; nevertheless, further investigationmay find that under certain circumstances the method may be optimized byconducting it at a particular temperature and/or pressure range.

It will be appreciated that a goal is to remove all of the toxicmaterial from the sediment, but that as a practical matter, it may onlybe physically possible and/or economically prudent to remove somewhatless than 100 wt % of the toxic material. However, even in such casesthe method will be considered successful because some toxic material hasbeen removed. More particularly, in one non-limiting embodiment, atleast 25 wt % of the toxic material is removed; alternatively at least27 wt % is removed; in another non-limiting version at least 40 wt %, orat least 50 wt %, or at least 60 wt %, or at least 70 wt %, or at least80 wt %, or at least 90 wt %; alternatively at least 95 wt %, and in adifferent non-limiting embodiment at least 99 wt %.

It will be appreciated that in one non-restrictive version the methoddescribed herein may be accomplished in the absence of lead slag mineralwool, where the lead slag mineral wool is or is not coated with an oilsoluble-hydrophobic film. In a different non-limiting embodiment themethod described herein may be practiced in the absence of rock flour.

In one non-limiting embodiment, the substance treated that contains atleast one toxic material may contain other materials, such as certainother water-soluble materials, and the basalt may selectively remove theat least one toxic material from the substance while not appreciablyremoving the other water-soluble materials.

The following examples are provided to illustrate the invention. Theexamples are not intended to limit the scope of the invention and theyshould not be so interpreted. Amounts are in weight parts or weightpercentages unless otherwise indicated.

EXAMPLES Example 1 Clean Water and Sand

The method concept was proven using clean water and blank sand spikedwith a Laboratory Control Spike (LCS) of toxic material. The procedurewas as follows.

-   -   1. First a solid basalt fiber sample was soaked in a 10% NaOH        (˜2N) solution for 30 minutes, and rinsed thoroughly with DI        water to remove excess sodium hydroxide and dried.    -   2. 60 grams of blank sand was spiked with 2 mL LCS/matrix spike        prepared at standard concentration using acetone. The mixture        was homogenized well, and then evaporated under a hood for 1-2        hours.    -   3. The sand was placed in the bottom of a 2 liter beaker.    -   4. A piece of the basalt fiber was cut a little smaller than the        beaker circumference using well-cleaned scissors. The size of        the basalt fiber piece was measured and recorded. The piece was        placed on top of the sand.    -   5. One liter of DI water was added on top of sand and basalt        filter in beaker. The top was covered with foil.    -   6. The beaker was gently agitated on a shaker on low speed over        a weekend. The speed was low to avoid the beaker coming out of        the shaker.    -   7. The basalt filter was propped over the beaker with a clean        apparatus so the water retained in the filter was allowed to        drip down back into the beaker.    -   8. The basalt filter was dried out under a hood on clean foil to        avoid contamination. It was allowed to dry.    -   9. The water was decanted from the container. The volume of the        decanted water was measured and recorded on a benchsheet.    -   10. The water sample was extracted for dioxins/furans according        to Method 1613B. It was treated as a regular sample. Batch alone        with MB (Method Blank), LCS, and DLCS (Duplicate Laboratory        Control Spike). Labeled standard was used.    -   11. The dried basalt fiber sample that soaked was extracted on a        soxhlet in toluene according to the method SOP protocol for        1613B. This was batched along with the sand sample. MB, LCS and        DLCS were used. They were spiked just like a normal batch.    -   12. 30 grams wet weight of the sand were extracted from the        bottom of the container. Total solids test was run as well. They        were put in the same batch with the filter.    -   13. Three sets of results were reported for testing of the        water, the basalt fiber sample portion that soaked in the spiked        sand/water, and 30 grams of the sand from the bottom of the        beaker.

The results of Example 1 are presented in Table III. In one instance,for OCDD, the amount recovered was 55%, which was calculated by dividingthe total recovered of 21905 picograms (pg) by the total spiked (40000pg)×100. Thus, the average total recovered was 63%. In Table III, notethat the abbreviation “Rec” refers to “recovered”.

TABLE III Comparison Chart - Clean Water and Sand Water Water BasaltBasalt (total Sand Total Basalt (initial Sample Rec Fiber recovered)Sand Rec Total Spike Amt Recovered spike) Contaminant (pg) (%) (pg) (%)(pg) (%) (pg) (pg) (%) (%) TCDD 484 19 1694 65 412 16 2589 4000 65 42PeCDD 2827 22 7544 58 2544 20 12914 20000 65 38 HxCDD 2896 23 7094 552837 22 12827 20000 64 35 HxCDD 2863 23 6975 55 2851 22 12688 20000 6335 HxCDD 2901 24 6512 53 2841 23 12254 20000 61 33 HpCDD 2412 21 6224 533099 26 11735 20000 59 31 OCDD 3607 16 11287 52 7011 32 21905 40000 5528 TCDF 563 20 1845 66 409 15 2816 4000 70 46 PeCDF 2594 21 7213 59 251920 12326 20000 62 36 PeCDF 3106 23 7751 58 2575 19 13432 20000 67 39HxCDF 2760 21 7175 56 2979 23 12915 20000 65 36 HxCDF 2625 21 6744 552875 23 12244 20000 61 34 HxCDF 2659 21 6710 54 3059 25 12428 20000 6234 HxCDF 3024 23 7147 54 2979 23 13150 20000 66 36 HpCDF 2355 19 6614 543359 27 12328 20000 62 33 HpCDF 2514 21 6283 53 3098 26 11895 20000 5931 OCDF 3923 15 14378 54 8571 32 26872 40000 67 36 Average 2595 17 701156 3177 24 12783 20471 63 35

Example 2 SJWP (San Jacinto Waste Pits) Sample

The procedure for testing similarly to Example 1 using a SJWP sample wasas follows.

-   -   1. First a solid basalt fiber sample was soaked in a 10% NaOH        (-2N) solution for 30 minutes, and rinsed thoroughly with DI        water to remove excess sodium hydroxide and dried.    -   2. 60 grams of native SJWP sediment known to contain        dioxins/furans was measured. The mixture was homogenized well.    -   3. The sand was placed in the bottom of a 2 liter beaker.    -   4. A piece of the basalt fiber was cut a little smaller than the        beaker circumference using well-cleaned scissors. The size of        the basalt fiber piece was measured and recorded. The piece was        placed on top of the sand.    -   5. One liter of DI water was added on top of the sediment sample        and basalt filter in beaker. The top was covered with foil.    -   6. The beaker was gently agitated on a shaker on low speed over        a weekend. The speed was low to avoid the beaker coming out of        the shaker.    -   7. The basalt filter was propped over the beaker with a clean        apparatus so the water retained in the filter was allowed to        drip down back into the beaker.    -   8. The basalt filter was dried out under a hood on clean foil to        avoid contamination. It was allowed to dry.    -   9. The water was decanted from the container. The volume of the        decanted water was measured and recorded on a benchsheet.    -   10. The water sample was extracted for dioxins/furans according        to Method 1613B. It was treated as a regular sample. Batch alone        with MB, LCS, and DLCS. Labeled standard was used.    -   11. The dried basalt fiber sample that soaked was extracted on a        soxhlet in toluene according to the method SOP protocol for        1613B. This was batched along with the sand sample. MB, LCS and        DLCS were used. They were spiked just like a normal batch along        with the sediment sample.    -   12. 30 grams wet weight of the sediment sample were extracted        from the bottom of the container. Total solids test was run as        well. They were put in the same batch with the filter. This was        batched along with another aliquot of 30 grams of the sediment        sample prior to experiment for comparison.    -   13. Three sets of results were reported for testing of the        water, the basalt fiber sample portion that soaked in the        sediment/water, and 30 grams of the sand from the bottom of the        beaker. The sediment sample prior to experiment results was also        reported.

The results are compared to the original sediment sample, which wasanalyzed separately to estimate the level of dioxins/furans in thesediment sample prior to exposure in water to the basalt fiber sample.Results are compared in Table IV which reflects all results reported inpicograms, unadjusted for sample size since that changes the reportingunits to concentrations and the units will differ between solid andliquid matrices.

The total percent recovery value is 200% since 60 grams of sediment wasused in the experiment compared to 30 grams of sediment used for theanalysis of the sediment prior to experimentation. Therefore totaldioxins/furans concentrations present in the sediment, filter and waterfrom the experiment should be approximately double that found in theoriginal sediment analyzed prior to experimentation. Using OCDD forcomparison, it may be noticed that the percent recovery is almostexactly 200% at 203%. The sum of the picograms recovered for the water,basalt fiber and sediment sample is 67,333.897 picograms which isapproximately double what was recovered in the sediment sample prior toexperimentation at 33,157.346. This is what was expected since doublethe sediment was used in the experiment sample at 60 grams compared to30 grams of sediment sample used prior to experimentation.

If only considering the total sum of 67,333.897 picograms recovered ofOCDD from the experiment from all three matrices, the percent of OCDD inthe sediment, water and basalt fiber is revealed as follows: 21% A inthe water from the experiment, 27% in the basalt fiber from theexperiment and 51% recovered from the sediment leftover in the bottom ofthe container post experiment.

It may be noted that although 60 grams of sediment was used in theexperiment, only 30 grams was found in the bottom of the container afterthe experiment was finished and the water was decanted out of thecontainer. This was due to half of the particulates from the sedimentdistributed as either suspended in the water or trapped in the pores ofthe basalt sample. It was not possible from the steps taken in Example 2to determine how much of the sediment is suspended in the aqueousportion and how much is trapped in the basalt filter. It is alsoinconclusive whether or not the basalt fiber is adsorbing dioxins/furans(removing dioxins/furans from the sediment) or if the recoveriesdetected in the basalt fiber are due to sediment particles trapped inthe filter which are contaminated with dioxins/furans.

Therefore this test was inconclusive regarding the adsorption ofdioxins/furans by the basalt fiber from an actual sediment sample knownto contain dioxins/furans because the sediment samples may have beenold. Thus, further investigation is necessary. Nevertheless, it appearsthat the basalt filter adsorbed at least 27% of the dioxins/furans.

TABLE IV SJWP Sample Total (Water + Sediment Sample Basalt FiberSediment Fiber + Sediment) (prior to Experiment) Water (pg) (pg) (pg)(pg) (pg) % recovered* TCDD 22.709 105.131 263.218 391.058 119.992 326%PeCDD 16.58 3.087 10.673 30.34 20.291 150% 1, 2, 3, 4, 7, 8-HxCDD 15.9134.351 11.902 32.166 25.511 126% 1, 2, 3, 6, 7, 8-HxCDD 20.11 10.63925.255 56.004 35.492 158% 1, 2, 3, 7, 8, 9-HxCDD 19.368 11.375 25.97556.718 35.047 162% 1, 2, 3, 4, 6, 7, 8-HpCDD 348.546 476.195 858.0691682.81 777.107 217% OCDD 14313.384 18325.278 34695.235 67333.89733157.346 203% TCDF 48.95 325.231 870.818 1244.999 340.737 365% PeCDF12.259 8.819 25.281 46.359 24.153 192% PeCDF 16.975 9.027 29.075 55.07735.349 156% HxCDF 21.496 16.68 38.965 77.141 39.893 193% 1, 2, 3, 6, 7,8-HxCDF 15.114 6.262 16.67 38.046 23.981 159% 1, 2, 3, 7, 8, 9-HxCDF15.041 2.942 10.74 28.723 18.126 158% 2, 3, 4, 6, 7, 8-HxCDF 18.4324.113 13.988 36.533 25.524 143% 1, 2, 3, 4, 6, 7, 8-HpCDF 50.49 58.362103.452 212.304 102.852 206% 1, 2, 3, 4,7, 8, 9-HpCDF 14.091 7.02 18.14439.255 20.784 189% OCDF 375.864 596.58 1165.733 2138.177 904.028 237%*Total % Recovered: When compared to Sediment levels prior to experiment*Note that total would be 200% since 60 grams was used for theexperiment compared to 30 grams used for sediment sample analysis priorto experiment.

Example 3 Heavy Metals Analysis Sample Preparation Step 1:

A large section (44.6 grams) of a 20 mm basalt needlepunch mat wassubmerged in a 2N sodium hydroxide solution and soaked for 30 minuteswhile stirring. This procedure removed a coating from the sample(sizing). The sample was thoroughly rinsed in deionized (DI) water toremove any the excess sodium hydroxide. The sample then dried overnightin a 105° C. forced air drying oven. This sample was considered thebaseline.

Three subsamples were then digested in concentrated nitric acid in a 95°C. hot block for 2 hours. Due to the nature of the material, the sampledid not completely digest and this analysis is considered a leachingprocedure. The resulting leachate was diluted and analyzed in comparisonwith known ICP-MS standards. Table V gives the results for the analysisof the baseline basalt sample. The initial material contains lead (Pb)and copper (Cu) in low amounts. LOQ refers to limit of quantification.

TABLE V Results for the Analysis of the Baseline Basalt Sample Limit ofQuantitation Parameter Result (μg/kg) (μg/kg) Arsenic (As) <LOQ 0.38Copper (Cu) 14.05 0.38 Mercury (Hg) <LOQ 0.15 Lead (Pb)  1.78 0.38

Sample Preparation Step 2:

Two subsamples of the previously prepared sample were weighed toapproximately 1 gram. A known solution of 10 μg/kg of each As, Cu, Pband 5 μg/kg Hg was prepared and divided into three tubes at volumes ofapproximately 50 mL each. The subsamples were added to two of the tubesand one tube was left as a control, labeled blank solution in the tableabove.

The closed three tubes were allowed to sit at room temperature for 24hours. The three solutions were then analyzed in comparison with knownICP-MS standards. The purpose of this process was to observe the changein concentrations of the As, Cu, Pb and Hg elements from the solutiondue to the interaction with the baseline sample material (calculated asgain “+” or depletion “−”). The results are shown in Table VI.

TABLE VI Results for the 24 Hour Soak of the Basalt Samples SamplePercent Change in Blank Solution After Solution After 24 ConcentrationParameter 24 Hours (μg/kg) Hours (μg/kg) (%) As 10.02 10.79 +7.7% Cu10.37 10.56 +1.8% Hg 5.13 5.43 +5.8% Pb 10.02 9.92 −1.0%

Sample Preparation Step 3:

For a more comprehensive understanding of the behavior of the basaltmaterial in contact with the solution, a larger initial sample aliquotand longer interaction time were employed.

The remaining previously prepared sample was weighed to approximately 30grams. A known solution of 10 μg/kg of each As, Cu, Pb and 5 μg/kg Hgwas prepared and divided into two beakers at volumes of approximately250 mL each. The subsample was added to one of the beakers and the otherbeaker was left as a control, labeled blank solution in the Table Vabove.

The covered beakers were allowed to sit at room temperature for 96hours. The three solutions were then analyzed in comparison with knownICP-MS standards. The purpose of this process was to observe the changein concentrations of the As, Cu, Pb and Hg elements from the solutiondue to the interaction with the baseline sample material (calculated asgain “+” or depletion “−”). The results are presented in Table VI, andit may be readily seen that arsenic and mercury were substantiallyremoved; notice the percent change in the last column for each of thesematerials, −18.4% and −57.5%, respectively.

TABLE VII Results for the 96 Hour Soak of the Basalt Sample SampleSolution Percent Change in Blank Solution After After 96 HoursConcentration Parameter 96 Hours (μg/kg) (μg/kg) (%) As 11.63 9.49−18.4% Cu 14.06 71.70  +410% Hg 6.23 2.65 −57.5% Pb 9.53 18.04 +89.3%

Example 4 Heavy Metals Analysis Sample Preparation Step 1:

A large section (111.2 grams) of the as-received needlepunch basalt mat(20 mm) was submerged in a 2N sodium hydroxide solution and soaked for30 minutes while stirring. This procedure removed a coating from thesample (sizing). The sample was thoroughly rinsed in deionized water toremove any the excess sodium hydroxide. The sample was then driedovernight in a 105° C. forced air drying oven. This sample is consideredthe baseline.

The sized and dried sample was divided into six portions for the sixanalyses requested. Sample numbers were assigned to the stripped anddried portions as follows:

-   -   A: Sized/Dried/Bulk sample for polychlorinated biphenyls (PCBs)        analysis=PCBs' baseline sample    -   B: Sized/Dried/As-received/Bulk sample for semi-volatile organic        compounds (SVOCs) analysis=SVOCs' baseline sample    -   C: Sized/Dried/Bulk sample for metals analysis=Metals' baseline        sample    -   D: Leached solution for polychlorinated biphenyls (PCBs)        analysis=PCBs' sample    -   E: Leached solution for semi-volatile organic compounds (SVOCs)        analysis=SVOCs' sample    -   F: Leached solution for metals analysis=Metals' sample

Three subsamples of Sample C were then digested in concentrated nitricacid in a 95° C. hot block for 2 hours. Due to the nature of thematerial, the sample did not completely digest and this analysis isconsidered a leaching procedure. The resulting leachate was diluted andanalyzed in comparison with known ICP-MS standards. The results arepresented in Tables VIII (ARO-CLOR PCBs), IX(bis(2-ethylhexyl)phthalate), and X (metals), below.

TABLE VIII Results for PCBs Baseline - Sample A Analyte Result (mg/kg)Reporting Limit (mg/kg) AROCLOR-1016 ND 0.93 AROCLOR-1260 ND 0.93

TABLE IX Results for bis(2-Ethylhexyl)phthalate SVOC Baseline - Sample BAnalyte Result (mg/kg) Reporting Limit (mg/kg) Bis (2-ethylhexyl)phthalate ND 2.5

TABLE X Results for Metals Baseline - Sample C Reporting Limit AnalyteResult (μg/kg) (μg/kg) Chromium (Cr) 1258 66 Copper (Cu) 1282 66 Nickel(Ni) 2200 197 Zinc (Zn) 2370 197 Cadmium (Cd) < LOQ 66 Arsenic (As) <LOQ 66 Mercury (Hg) < LOQ 66

Sample Preparation Step 2:

One liter leaching solutions were prepared to the followingconcentrations:

1 μg/L PCBs standards (AROCLOR-1016 and AROCLOR-1260)

100 μg/L SVOC (Bis (2-ethylhexyl) phthalate)

10 μg/L of each of the metals Cr, Cu, Ni, Zn, Cd, As and 7.5 μg/kg Hg

The sized and dried bulk sample was cut into three sections.Approximately 16 gram portions were used for the PCBs and SVOCs leach,and 50 grams were used for the metals analysis. The three portions weresubmerged in their respective leaching solutions. The solutions werecovered and allowed to sit at room temperature for 24 hours.

The PCB's and SVOC's solutions were poured into amber bottles andsubmitted to the chemistry department as samples D and E.

The metals solution was then analyzed in comparison with known ICP-MSstandards. A blank solution was also utilized.

The purpose of this process was to observe the change in concentrationsof the analytes from the solution due to the interaction with thebase-line sample material (calculated as gain “+” or depletion “−”).

TABLE XI Results for 24 Hours PCBs Soak of the Basalt Sample SampleSolution Percent Change in Blank Solution After 24 Hours ConcentrationParameter (μg/L) (μg/L) (%) AROCLOR-1016 1 0.34 −66% AROCLOR-1260 1 0.20−80%

TABLE XII Results for 24 Hours SVOC Soak of the Basalt Sample SampleSolution Percent Change in Blank Solution After 24 Hours ConcentrationParameter (μg/L) (μg/L) (%) Bis (2-ethylhexyl) 100 39 −61% phthalate

TABLE XIII Results for 24 Hours Metals Soak of the Basalt Sample BlankSolution Sample Solution Percent Change in Parameter (μg/L) After 24Hours (μg/L) Concentration (%) Cr 13.96 2.79 −80% Cu 16.00 3.95 −75% Ni14.09 7.61 −46% Zn 17.28 6.47 −63% Cd 14.13 4.92 −48% As 14.39 7.47 −48%Hg 8.06 3.80 −53%

It may be seen from the results presented in Tables XI, XII, and XIIIthat basalt can remove PCBs, bis(2-ethylhexyl)phthalate, and metals,respectively from aqueous solutions.

Further, it will be appreciated that while the results presented inTable VII indicate an increase in concentration of copper and lead, ithas been found that in other experiments that copper and lead have beenremoved.

Example 5 Heavy Metals Analysis Sample Preparation Step 1:

The as-received needle punch basalt mats, ¼-inch thick (0.64 cm) and½-inch thick (1.3 cm) were submerged in a 2N sodium hydroxide solutionand soaked for 30 minutes while stirring. This procedure removed acoating from the sample (sizing). The samples were thoroughly rinsed indeionized water to remove any the excess sodium hydroxide. The sampledwere then dried overnight in a 105° C. forced air drying oven. Thesesamples were considered the baseline.

The sized and dried sample was divided into four portions for the fouranalyses requested. Sample numbers were assigned to the stripped anddried portions as follows:

-   -   A and B: Sized/Dried/Bulk sample for metals analysis=Metals'        baseline sample    -   C and D: Leached solution for metals analysis=Metals' sample

Two subsamples of Samples A/C and two subsamples of Samples B/D werethen digested in concentrated nitric acid in a 95° C. hot block for 2hours. Due to the nature of the material, the sample did not completelydigest and this analysis is considered a leaching procedure. Theresulting leachate was diluted and analyzed in comparison with knownICP-MS standards. The results for the Metals Baseline are presented inTables XIV and XV, below.

TABLE XIV Results for Metals Baseline - Sample A ¼-inch (0.64 cm) BasaltNeedle Punch Mat Reporting Limit Analyte Result (μg/kg) (μg/kg) Chromium(Cr) 827.7 80 Copper (Cu) 331.1 80 Nickel (Ni) 7229 400 Zinc (Zn) 169480 Cadmium (Cd) <LOQ 80 Arsenic (As) <LOQ 80 Mercury (Hg) <LOQ 80 Lead (<LOQ 80

TABLE XV Results for Metals Baseline - Sample B ½-inch thick (1.3 cm)Basalt Needle Punch Mat Analyte Result (μg/kg) Reporting Limit (μg/kg)Chromium (Cr) 280.1 80 Copper (Cu) 299.5 80 Nickel (Ni) 450.6 80 Zinc(Zn) 1388 80 Cadmium (Cd) < LOQ 80 Arsenic (As) < LOQ 80 Mercury (Hg) <LOQ 80 Led (Pb) 138.2 80

Sample Preparation Step 2:

One liter leaching solutions were prepared to the followingconcentrations:

10 μg/L of each of the metals Cr, Cu, Ni, Zn, Cd, As, Hg, and Pb

The sized and dried bulk sample was cut into three sections.Approximately 6.7 grams of sample C were used for the metals.Approximately 20.5 grams of Sample D were used for the metals. The threeportions were submerged in their respective leaching solutions. Thesolutions were covered and allowed to sit at room temperature for 24hours.

The metals solution was then analyzed in comparison with known ICP-MSstandards. A blank solution was also utilized.

The purpose of this process was to observe the change in concentrationsof the analytes from the solution due to the interaction with thebase-line sample material (calculated as gain “+” or depletion “−”).

TABLE XVI Results for 24 Hours Metals Soak of the Basalt Sample C ¼-inch(0.64 cm) Basalt Needle Punch Mat Blank Solution Sample Solution PercentChange in Parameter (μg/L) After 24 Hours (μg/L) Concentration (%) Cr8.52 2.59 −70% Cu 13.96 8.67 −38% Ni 9.18 10.85 +18% Zn 19.16 21.08 +10%Cd 8.83 8.51 −3.6%  As 8.35 0.69 −92% Hg 8.78 8.79  0% Pb 11.87 1.19−90%

TABLE XVI Results for 24 Hours Metals Soak of the Basalt Sample C ½-inchthick (1.3 cm) Basalt Needle Punch Mat Blank Solution Sample SolutionPercent Change in Parameter (μg/L) After 24 Hours (μg/L) Concentration(%) Cr 8.52 2.75 −68% Cu 13.96 1.91 −86% Ni 9.18 5.94 −35% Zn 19.16 6.61−66% Cd 8.83 3.29 −63% As 8.35 7.66 −8.3%  Hg 8.78 8.73 −0.5%  Pb 11.871.19 −91%

Thus, Tables XVI and XVII demonstrate a 90% and 91% lead absorption bybasalt.

In the foregoing specification, the invention has been described withreference to specific embodiments thereof, and has been described aseffective in providing methods for removing toxic materials fromsubstances such as sediments. However, it will be evident that variousmodifications and changes can be made thereto without departing from thebroader scope of the invention as set forth in the appended claims.Accordingly, the specification is to be regarded in an illustrativerather than a restrictive sense. For example, specific fluids,substances, sediments, toxic materials, basalt forms, proportions,contact times, contact methods, etc. falling within the claimedparameters, but not specifically identified or tried in a particularprocess, are expected to be within the scope of this invention.Additionally, the methods described herein may be expected to removetoxic material from any substance that also comprises or consists ofwater and at least one toxic material.

The present invention may suitably comprise, consist or consistessentially of the elements disclosed and may be practiced in theabsence of a disclosed element or in the absence of an element notdisclosed. For instance, there may be provided a method of removingtoxic material from a substance, e.g. sediment, that consistsessentially of or consists of contacting sediment comprising, consistingessentially of or consisting of water and at least one toxic materialwith an effective amount of basalt for a period of time effective toremove at least a portion of the at least one toxic material from thesediment by adsorption, including, but not necessarily limited to, theat least one toxic materials, the periods of time, and the amounts setforth in the claims.

As used herein, the terms “comprising,” “including,” “containing,”“characterized by,” and grammatical equivalents thereof are inclusive oropen-ended terms that do not exclude additional, unrecited elements ormethod acts, but also include the more restrictive terms “consisting of”and “consisting essentially of” and grammatical equivalents thereof. Asused herein, the term “may” with respect to a material, structure,feature or method act indicates that such is contemplated for use inimplementation of an embodiment of the disclosure and such term is usedin preference to the more restrictive term “is” so as to avoid anyimplication that other, compatible materials, structures, features andmethods usable in combination therewith should or must be, excluded.

As used herein, the singular forms “a,” “an,” and “the” are intended toinclude the plural forms as well, unless the context clearly indicatesotherwise.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items.

As used herein, relational terms, such as “first,” “second,” “top,”“bottom,” “upper,” “lower,” “over,” “under,” etc., are used for clarityand convenience in understanding the disclosure and accompanyingdrawings and do not connote or depend on any specific preference,orientation, or order, except where the context clearly indicatesotherwise.

As used herein, the term “substantially” in reference to a givenparameter, property, or condition means and includes to a degree thatone of ordinary skill in the art would understand that the givenparameter, property, or condition is met with a degree of variance, suchas within acceptable manufacturing tolerances. By way of example,depending on the particular parameter, property, or condition that issubstantially met, the parameter, property, or condition may be at least90.0% met, at least 95.0% met, at least 99.0% met, or even at least99.9% met.

As used herein, the term “about” in reference to a given parameter isinclusive of the stated value and has the meaning dictated by thecontext (e.g., it includes the degree of error associated withmeasurement of the given parameter).

What is claimed is:
 1. A method for removing toxic material from asubstance, the process comprising: contacting the substance, where thesubstance comprises water and at least one toxic material, with aneffective amount of basalt for a period of time effective to remove atleast a portion of the at least one toxic material from the substanceinto the basalt.
 2. The method of claim 1 where the substance issediment.
 3. The method of claim 2 where the basalt is in the form of aliner, a cap, a filter, and combinations thereof.
 4. The method of claim1 where removing the at least a portion of the at least one toxicmaterial from the substance into the basalt comprises the basaltadsorbing the at least one toxic material.
 5. The method of claim 1where the basalt is in a form selected from the group consisting offibers, chopped fibers, roving, filaments, mats, strands, choppedstrands, particles, pellets, textiles, fabrics, tape, yarn, mesh, wooland combinations thereof.
 6. The method of claim 1 where toxic materialis selected from the group consisting of dioxins, furans,polychlorinated biphenyls (PCBs), bis(2-ethylhexyl)phthalate, arsenic,mercury, chromium, copper, nickel, zinc, cadmium, lead, and combinationsthereof.
 7. The method of claim 1 where effective amount of basalt tothe at least one toxic material ranges from about 200:1 to about 1:3 ona weight : weight basis.
 8. The method of claim 1 where effective amountof basalt to the at least one toxic material ranges from about 100:1 toabout 1:2 on a weight : weight basis.
 9. The method of claim 1 where theeffective amount of time ranges from about 24 hours to about 7 days. 10.The method of claim 1 where the effective amount of time ranges fromabout 2 days to about 6 days.
 11. The method of claim 1 where theportion of the at least one toxic material removed is at least 25 wt %.12. The method of claim 1 where the portion of the at least one toxicmaterial removed is at least 40 wt %.
 13. The method of claim 1 wherethe portion of the at least one toxic material removed is at least 55 wt%.
 14. The method of claim 1 where the substance additionally comprisesat least one water-soluble material, and where the at least one toxicmaterial is an organic compound and the basalt selectively adsorbs theat least one toxic material and does not appreciably adsorb the at leastone water-soluble material.
 15. A method for removing toxic materialfrom a sediment, the process comprising: contacting the sediment, wherethe sediment comprises water and at least one toxic material, with aneffective amount of basalt for a period of time effective to remove atleast a portion of the at least one toxic material from the sedimentinto the basalt, where removing the at least a portion of the at leastone toxic material from the substance into the basalt comprises thebasalt adsorbing the at least one toxic material; where toxic materialis selected from the group consisting of dioxins, furans,polychlorinated biphenyls (PCBs), bis(2-ethylhexyl)phthalate, arsenic,mercury, chromium, copper, nickel, zinc, cadmium, lead, and combinationsthereof.
 16. The method of claim 15 where effective amount of basalt tothe at least one toxic material ranges from about 200:1 to about 1:3 ona weight : weight basis.
 17. The method of claim 15 where the portion ofthe at least one toxic material removed is at least 25 wt %.
 18. Amethod for removing toxic material from a sediment, the processcomprising: contacting the sediment, where the sediment comprises waterand at least one toxic material, with an amount of basalt to the atleast one toxic material ranges from about 200:1 to about 1:3 on aweight : weight basis to remove at least a portion of the at least onetoxic material from the sediment into the basalt, where removing the atleast a portion of the at least one toxic material from the substanceinto the basalt comprises the basalt adsorbing the at least one toxicmaterial; where toxic material is selected from the group consisting ofdioxins, furans, polychlorinated biphenyls (PCBs),bis(2-ethylhexyl)phthalate, arsenic, mercury, chromium, copper, nickel,zinc, cadmium, lead, and combinations thereof, and where the basalt isin a form selected from the group consisting of fibers, chopped fibers,roving, filaments, mats, strands, chopped strands, particles, pellets,textiles, fabrics, tape, yarn, mesh, wool and combinations thereof. 19.The method of claim 18 where the contacting ranges from about 24 hoursto about 7 days.
 20. The method of claim 18 where the portion of the atleast one toxic material removed is at least 25 wt %.